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Updated: Aug 26, 2025

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
Ligand non-innocence allows isolation of a neutral and terminal niobium nitride
Shuruthi Senthil1, Seongyeon Kwon2,3, Hoyoung Im2,3
1Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA. mindiola@sas.upenn.edu.
Abstract:
Complex (PNP)NbCl2(N[Bu]Ar) (1) (PNP- = N[2-PiPr2-4-methylphenyl]2; Ar = 3,5-Me2C6H3) reacts with one equiv. of NaN3 to form a mixture of (PNPN)NbCl2(N[Bu]Ar) (2) and (PNP)NbN(N[Bu]Ar) (3), both of which have been spectroscopically and crystallographically characterized, including 15N isotopic labelling studies. Complex 3 represents the first structurally characterized example of a neutral and mononuclear Nb nitride. Independent studies established 3 to form via two-electron reduction of 2, whereas oxidation of 3 by two-electrons reversed the process. Computational studies suggest the transmetallation step to produce the intermediate [(PNP)NbCl(N3)(N[Bu]Ar)] (A) which extrudes N2 to form the phosphinimide [(PNPN)NbCl(N[Bu]Ar)] (B) followed by disproportionation to 2 and low-valent [(PNPN)Nb(N[Bu]Ar)] (C). The latter then undergoes intramolecular N-atom transfer to form the nitride moiety in 3.
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